EP0497567A2 - Objet en caoutchouc revêtu pour applications sanitaires - Google Patents

Objet en caoutchouc revêtu pour applications sanitaires Download PDF

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Publication number
EP0497567A2
EP0497567A2 EP19920300731 EP92300731A EP0497567A2 EP 0497567 A2 EP0497567 A2 EP 0497567A2 EP 19920300731 EP19920300731 EP 19920300731 EP 92300731 A EP92300731 A EP 92300731A EP 0497567 A2 EP0497567 A2 EP 0497567A2
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EP
European Patent Office
Prior art keywords
rubber
resin
cyclic
rubber article
sanitary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP19920300731
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German (de)
English (en)
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EP0497567B1 (fr
EP0497567A3 (en
Inventor
Morihiro Sudo
Tomoyasu Muraki
Eiji Kawachi
Yasushi Kawachi
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DAIKYO GOMU SEIKO Ltd
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DAIKYO GOMU SEIKO Ltd
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Priority claimed from JP3336690A external-priority patent/JP2895293B2/ja
Application filed by DAIKYO GOMU SEIKO Ltd filed Critical DAIKYO GOMU SEIKO Ltd
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Publication of EP0497567A3 publication Critical patent/EP0497567A3/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/315—Pistons; Piston-rods; Guiding, blocking or restricting the movement of the rod or piston; Appliances on the rod for facilitating dosing ; Dosing mechanisms
    • A61M5/31511—Piston or piston-rod constructions, e.g. connection of piston with piston-rod
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D51/00—Closures not otherwise provided for
    • B65D51/18—Arrangements of closures with protective outer cap-like covers or of two or more co-operating closures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/14—Details; Accessories therefor
    • A61J1/1468—Containers characterised by specific material properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/315—Pistons; Piston-rods; Guiding, blocking or restricting the movement of the rod or piston; Appliances on the rod for facilitating dosing ; Dosing mechanisms
    • A61M5/31511—Piston or piston-rod constructions, e.g. connection of piston with piston-rod
    • A61M5/31513—Piston constructions to improve sealing or sliding
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/315—Pistons; Piston-rods; Guiding, blocking or restricting the movement of the rod or piston; Appliances on the rod for facilitating dosing ; Dosing mechanisms
    • A61M5/31511—Piston or piston-rod constructions, e.g. connection of piston with piston-rod
    • A61M5/31515—Connection of piston with piston rod
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S220/00—Receptacles
    • Y10S220/19—Rubber plugs and caps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31826—Of natural rubber
    • Y10T428/31833—Next to aldehyde or ketone condensation product or addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31924—Including polyene monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31931—Polyene monomer-containing

Definitions

  • This invention relates to sanitary laminated rubber articles suitable for use as various articles with safety and sanitary property, for example, containers for foods or pharmaceutical chemicals, transporters, instruments, packaging materials and the like.
  • the rubber article of the present invention has very excellent properties which can be adapted to the standard test values of various official documents, required in this field, and can further satisfy the test items having lately become an important problem from the pharmaceutical standpoint and has good economical property.
  • JP 11 Japanese Pharmacopoeia
  • ISO International Standards Organization
  • EP European Pharmacopoeia
  • USP West Germany Industrial Standard DIN 58, 366-58, 368 (DIN), British Standard 3263 (BS), etc.
  • test items and higher standards from medical standpoint have lately been taken into additional consideration.
  • test methods and quality standards are provided in Official Notification Nos. 300 and 301 (standards for blood-collecting equippments and blood-transfusion sets) of the Ministry of Health and Welfare and Official Notification Nos. 442 and 413 (standards for injection cylinders) of the Ministry of Health and Welfare.
  • IR isoprene rubber
  • BR butadiene rubber
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-terpolymer
  • IIR isobutylene-isoprene rubber
  • CIIR chlorinated rubber of IIR
  • BIIR brominated rubber of IIR
  • DIIR isobutylene-isoprene-divinylbenzene terpolymer
  • a rubber article for pharmaceutical chemicals and medical instruments comprising a rubber composition coated with a resin film
  • a technique of laminating a vulcanized rubber with a film of polypropylene (PP) (Utility Model Publication Nos. 5751/1969 and 27753/1969); a stopper wholly coated with a fluoro resin excellent in chemical resistance (Utility Model Publication No. 17831/1970); a rubber stopper covered with a trifluoroethylene resin on a surface in contact with a medical liquor (Utility Model Publication No.
  • a sanitary rubber article whose rubber surface is laminated with a resin film comprising a cyclic olefinic compound or bridged polycyclic hydrocarbon compound as a polymeric component.
  • Fig. 1 is a sectional view of one embodiment of the rubber article of the present invention, i.e. the whole surface being laminated with a cyclic resin film of the present invention.
  • Fig. 2 is a sectional view of another embodiment of the rubber article of the present invention, enclosed in a glass bottle charged with a medical liquor and fastened by an aluminum cap.
  • Fig. 3 is a sectional view of a further embodiment of the rubber article of the present invention, enclosed in an exterior support of a plastic container and covered by an upper cover, the laminated part of the rubber article being bonded by fusion with the exterior support and upper cover.
  • Fig. 4 is a sectional view of a slidable stopper fitted to an end of a push rod of a syringe, the stopper being laminated with a cyclic resin film of the present invention.
  • Fig. 5 is a sectional view of a slidable stopper laminated with a cyclic resin film of the present invention.
  • Fig. 6 is a sectional view of a rubber stopper for freeze drying, whose whose leg part is laminated with a fluoro resin and flange part is laminated with a cyclic resin film of the present invention.
  • Fig. 7 is a vertically sectional view of a rubber stopper whose leg part in contact with a liquid medicament and flange part are laminated with a cyclic resin film of the present invention.
  • Fig. 8 is a cross-sectional view of the laminated rubber stopper of Fig. 7 (Eglue type rubber stopper).
  • the present invention provides a sanitary rubber article whose rubber surface is laminated with a resin film comprising a cyclic olefinic compound or bridged polycyclic hydrocarbon compound as a polymeric component.
  • cyclic olefin compound monocyclic olefin compounds or alkyl or acrylate derivatives thereof are particularly preferable.
  • bridged polycyclic hydrocarbon compound those containing at least one unsaturated bond in the ring or substituent are particularly preferable.
  • a resin containing the above described cyclic olefin compound or the above described bridged polycyclic hydrocarbon compound as a polymeric component (which will hereinafter be referred to as "the cyclic resin" of the present invention) includes those containing, as a copolymeric component, lower olefins, aromatic hydrocarbons or aromatic vinyl monomers, and can be mixed with olefin resins.
  • the cyclic resin of the present invention more preferably has any one of properties, i.e. a bromine number of at most 5 and a softening point of at least 90 °C.
  • cyclopentadiene obtained from the C5 fractions prepared by cracking naphtha of petroleum fractions is a monomer obtained abundantly with a low cost on a commercial scale.
  • Dimerization of cyclopentadiene (CPD) at room temperature results in dicyclopentadiene (DCP), while thermal cracking of DCP at 140 to 160 °C gives CPD.
  • CPD and DCP as a raw material, petroleum resins are produced and applied to production of tackifiers as adhesives in the rubber industry, sizing agent resins for paper making, raw material resins for paints, etc.
  • the inventors have found that a rubber article whose surface is laminated with this resin is a very sanitary rubber article capable of passing the test of JP 11, etc.
  • the present invention is based on this finding.
  • cyclic resin of the present invention to be used as a polymeric component, are as follows:
  • Monocyclic olefin compounds such as,
  • Lower alkyl derivatives of the above described compounds containing 1 to 3 lower alkyl groups substituted, e.g. methyl group, ethyl group, etc, acrylate derivatives and the like.
  • bridged polycyclic hydrocarbon compound there are preferably used bridged polycyclic hydrocarbon compounds with two or more rings, in particular, bridged polycyclic olefin compounds or derivatives thereof and bridged poly ⁇ cyclic saturated hydrocarbon compounds having unsaturated bonds in the substituents, i.e. bridged polycyclic cycloalkene compounds and their lower alkyl derivatives, aryl derivatives, aralkyl derivatives, and bridged polycyclic cycloalkane compound vinyl derivatives, allyloxy derivatives, (meth)acryloxy derivatives, etc.
  • bridged polycyclic hydrocarbon compounds with two or more rings in particular, bridged polycyclic olefin compounds or derivatives thereof and bridged poly ⁇ cyclic saturated hydrocarbon compounds having unsaturated bonds in the substituents, i.e. bridged polycyclic cycloalkene compounds and their lower alkyl derivatives, aryl derivatives, aralkyl derivatives, and bridged polycyclic cycloalkane compound vinyl derivatives,
  • bicyclo[2,2,1]-2-heptene bicyclo[2,2,1]-2,5-heptadiene (2,5-norbornadiene) 6-ethyl-bicyclo[1,2,1]-2-heptene 6-ethylidene-bicyclo[2,2,1]-2-heptene (5-ethylidene-2-norbornene) 6-phenyl-bicyclo[2,2,1]-hepto-2-ene tricyclo[4,3,0,1 2. 5 ]-3-decene tricyclo[4,3,0,1 2.
  • cyclic resin of the present invention at least one member selected from the group consisting of cyclic olefin compounds and bridged polycyclic hydrocarbon compounds is used as a polymeric cocmponent and in addition, lower olefins, aromatic compounds or vinyl monomers of lower olefins or aromatic compounds capable of being copolymerizable with these polymeric components can be incorportaed as a copolymeric component.
  • the copolymeric component are ethylene, propylene, isoprene, butadiene, methylpentene, norbornene, butene, vinyltoluene and the like. These other copolymeric components can be used individually or in combination.
  • Polymerization of the cyclic resin of the present invention can be carried out in known manner, as disclosed in Japanese Patent Publication Nos. 11818/ 1972, 43412/1983, 1442/1986 and 19761/1987, and Japanese Patent Laid-Open Publication Nos. 75700/1975, 129434/1980, 127728/1983, 168708/1985, 115916/1986, 271308/1986, 22118/1988, 221118/1988, 243103/1988 and 180976/1990.
  • monomers such as olefin compounds or aromatic compounds can be added to form copolymers.
  • monomers such as olefin compounds or aromatic compounds.
  • the presence of monomers as the polymeric components, low molecular weight oligomers, metallic catalysts, etc. in the cyclic resin of the present invention causes generation of odors and degradation of the sanitary properties. This is unfavorable.
  • the cyclic resin of the present invention there is preferably used a resin capable of satisfying a softening point of at least 90°C (JIS K 2207, 2531, ring and ball method) and a bromine number of at most 5 (JIS K 2543). If the bromine number of the cyclic resin exceeds 5, coloration or discoloration will take place in a sanitary rubber article after laminated with the cyclic resin. In order to prevent the coloration or discoloration, an antioxidant is added.
  • antioxidants to be added to the cyclic resin of the present invention are 2-6-di-t-butyl-4-methylphenol(BHT), octadecycl-3-(4′-hydroxy-3′,5′-di-t-butylphenyl) propionate (commercial name: Irganox 1076, made by Chiba Geigy Co.), tetrakis[methylene(3,5-d-t-butyl-4-hydroxyphenyl) propionate]-methane (commercial name: Irganox 1010, made by Chiba Geigy Co.), tocophenol, 4,4′-thiobis(6-t-bytyl-3-methylphenol) (commercial name: Antage RC, made by Kawaguchi Kagaku KK), bis(2,2,6,6,-tetramethylpiperidyl) sebacate (commercial name: Sanol LS-770, made by Sanko KK), 1,3,8-triaza-7,7,9,9-(B
  • the content of the cyclic olefin monomer in the cyclic resin of the present invention is preferably at least 30 % by weight.
  • the cyclic resin has a molecular weight of 5,000 to 100,000,000.
  • the low molecular weight resin is a highly viscous material and the high molecular weight resin is a powdered material.
  • a working assistant As the working assistant, at least one of higher fatty acids, higher fatty acid esters, silicone oils, fluorinated oils and the like can be added in a proportion of 0 to 5 % by weight.
  • Lamination of a rubber surface with the cyclic resin of the present invention can be carried out by a method comprising dissolving the cyclic resin in a commonly used solvent, i.e. aliphatic or aromatic hydrocarbon solvents or mixtures thereof such as n-hexane, cyclohexane, butane, pentane, cyclooctane, heptane, ethylbenzene, propylbenzne and the like in a proportion of 1 to 8 % by weight, applying or spreading the solution to or on a rubber surface, or a method comprising forming the cyclic resin of the present invention in a film by a known technique, e.g. T-die method, elongation method, inflation method, etc. and then laminating the resulting film on a rubber surface.
  • a commonly used solvent i.e. aliphatic or aromatic hydrocarbon solvents or mixtures thereof such as n-hexane, cyclohexane,
  • the cyclic resin of the present invention can be mixed with an olefinic resin and laminated on a rubber surface.
  • at most 10 % by weight of a low to middle molecular weight polyethylene or polybutene can be used to improve the workability.
  • a method can be employed comprising forming the cyclic resin into a film of 0.1 to 1 mm in thickness, superimposing the film on a non-vulcanized rubber and then conducting simultaneously vulcanization and shaping of the rubber and lamination of the film, which method is economically preferable.
  • a method for example, there are a method described in Japanese Patent Publication No. 5046/1984 and a method comprising laminating a rubber stopper with a plurality of resin films, as disclosed in Japanese Patent Publication No. 53184/1982, the inventors have proposed.
  • the cyclic resin of the present invention can be applied to a rubber surface of a rubber stopper used for a plastic container, as disclosed in Japanese Patent Laid-Open Publication No. 1275/1990 and Japanese Patent Application No. 399/1990.
  • a laminated rubber article obtained by laminating a rubber body with the cyclic resin of the present invention in the form of a film can pass the standards provided in "44 Test Method of Plastic Container for Liquid Transfusion” and "43 Test Method of Rubber Stopper for Liquid Transfusion” of JP 11. It is found that a film of the cyclic resin of the present invention has very excellent resistance to water absorption, moisture absorption and moisture permeation.
  • the rubber to be laminated with the cyclic resin of the present invention there can be used commonly used rubbers such as natural rubber, IR, IIR, BR, EPDM, CR, NBR and the like, since the cyclic resin is capable of strongly bonding to the rubber surface and wrapping it even in the form of a very thin film and compounding agents in the rubber, e.g. vulcanizing agents, vulcanization accelerators, reinforcing agents do not come out of it, that is, the insaniatry substances contained in the rubber are not subject to elution and contamination of exterior contacted materials therewith, such as foods or pharmaceutical chemicals.
  • commonly used rubbers such as natural rubber, IR, IIR, BR, EPDM, CR, NBR and the like, since the cyclic resin is capable of strongly bonding to the rubber surface and wrapping it even in the form of a very thin film and compounding agents in the rubber, e.g. vulcanizing agents, vulcanization accelerators, reinforcing agents do not come out of it,
  • the cyclic resin of the present invention becomes a film with flexibility and elasticity and thus maintain the flexibility and elasticitycomparable to a rubber to be laminated therewith.
  • the product was added to 2000 ml of acetone-isopropyl alcohol (1 : 1) mixed solvent, to which 10 ml of hydrochloric acid was added to precipitate a resin, and the precipitated resin ras washed with the above described mixed solvent, thus obtaining 360 g of DCP ring-opened polymer.
  • the reaction product was subjected to centrifugal separation and filtration to remove the catalyst contained therein and precipitated in 1000 ml of a mixed solvent of acetone-isopropyl alcohol (1 : 1) to obtain 100 g of a resin (a) having a softening point of 136 °C and average molecular weight of about 30,000 and being soluble in n-hexane by 5 %.
  • the resin (a) was shaped in a film while adding 1.5 parts by weight of dimethylsiloxane and 1.5 part by weight of stearic acid sorbitan ester thereto.
  • a stirrer and dropping funnel were fitted to the center of a three neck flask of 5000 ml, being dried. 2500 ml of dehydrated toluene and 150 g of dehydrated DCP were charged in the flask, to which 31 g of ethylaluminum sesqui-chloride and 4.2 g of dichloroethoxyoxovanadium were added as catalysts and through which mixed gases of dry ethylene gas and nitrogen gas (1/2) was passed for 7 minutes and passed at 20 °C for 60 minutes. The polymerization ras conducted for 30 minutes.
  • the reaction product was subjected to centrifugal separation and filtration to remove the catalyst contained therein and precipitated in a large amount of mixed solvents of acetone-isopropyl alcohol (1 : 1) to obtain 60 g of a resin (b) having a softening point of 136 °C and a bromine number of 0.3.
  • copolymerized resin (b) was formed in a film after adding 3 % by weight of stearic acid sorbitan ester, 1 % by weight of dimethylpolysilioxane and 0.5 % by weight of BHT thereto. In the case of brushing or spraying, it was applied to a rubber surface in the form of a cyclohexane solution (5 % by weight).
  • the polymerized product was charged in an autoclave, to which 80 g of cyclohexane and 2 g of Raney nickel were added, and the mixture was subjected to hydrogenation at a hydrogen pressure of 100 kg/cm2 and a temperature of 200 °C for 4 hours. After cooling, the reaction product was filtered to remove the catalyst and distilled to remove the solvent. 0.7 % by weight of BHT was added thereto. The resulting resin (c) had a bromine number of 1.5, softening point of 122 °C and contained n-hexane insolubles.
  • the polymerized product was dissolved in 4500 ml of tetrahydrofuran, mixed with 23 g of a palladium-alumina catalyst containing 5 % by weight of palladium and then subjected to hydrogenation at a hydrogen pressure of 100 kg/cm2 and a temperature of 170°C for 5 hours. Then, the similar procedure to Example 1 was repeated to obtain a polymerized resin. 0.5 part by weight of BHT ras added thereto to obtain a resin (d) having a bromine number of 0.05 and a softening point of 112 °C.
  • the BR rubber compounding operations and vulcanization operations were carried out according to SRIS (Nippon Gomu Kyokai Kikaku-Japan Rubber Institute Standards-) 3603.
  • the vulcanization condition was 160 °C x 12 minutes.
  • the molded rubber article, having a shape of a rubber base 1, as shown in Fig. 1, was immersed in n-hexane solutions of the resins (a) to (g) of the present invention two or more times, coated with a film with a thickness of 0.1 mm and completely dried at a temperature of about 90 °C, thus forming a film shown in Fig. 1 on the rubber surface (Examples 1 to 8).
  • a sample is mixed with water in an amount of 10 times as much as the sample and then heated and extracted with high pressure steam at 121 °C for 1 hour.
  • DIN or BS is carried out by heating at 121 °C for 30 minutes, it is apparent that the extraction condition of JP 11 is the severest.
  • An injection cylinder fitted with a test needle [22 G (0.70 x 32 mm)] is charged with water and then pierced through a piercing position 8 20 times. At the 20th penetration, the water in the injection cyclinder is injected into the vial and the needle is then withdrawn. After vibrating the vial, the rubber stopper is removed, the content liquid is filtered and the number of rubber fragments on the filter paper is counted.
  • This test method is an improved method of BS.
  • BS provides that the number of rubber fragments be at most 3, but in this field, it has lately been desired that it should be at most 2.
  • a vial 4 of Fig. 2 is charged with 8 ml of a 2 wt % aqueous solution of NaCl, enclosed by a rubber stopper 3 and fastened by an aluminum cap 6.
  • This glass vial is steam-heated at 121 ⁇ 1 °C for 60 minutes in a pressure vessel and then allowed to stand for about 10 hours.
  • 5 ml of a sample gas is taken from a head space 7 of the vial using a syringe for gases and then subjected to analysis by a gas chromatography under conditions of column 10 % OV-101 (180-200 mesh WHP), carrier gas He 50 ml/min and column temperature 100-200 °C (raised at 4 °C /min), thus checking the presence or height of peaks.
  • This is a test for checking generation of gases in very small amounts from the rubber and additives to be blended, which has lately been considered important.
  • a vulcanized and shaped rubber article is dried at 105 °C at normal pressure for 3 hours, allowed to stand in a desiccator containing a drying agent for about 1 hour and the weight thereof (A) is then precisely measured. Then, the rubber stopper is immersed in purified water in an amount of 10 times as much as the rubber stopper and steam-heated, as it is, at 121 ⁇ 1 °C for 30 minutes in a pressure vessel. After cooling, only the rubber stopper is allowed to stand for 30 minutes in a desiccator to remove the water on the surface, at which the weight (B) thereof is measured. Thus, ⁇ [(B) - (A)/(A)] x 100 ⁇ (%) is calculated and a value of at most 2 % by weight is regarded as passing this test.
  • a rubber stopper is placed on a fluoro resin plate, and while one end of the plate is fixed, the other end thereof is raised at a constant rate to move the rubber stopper.
  • the angle of the plate, at which the rubber stopper starts to move, is measured.
  • the rubber stoppers laminated with the cyclic resin film of the present invention (Examples 1 to 5) satisfy the standards of JP 11 and are also more excellent in the special sanitary tests as shown in Table 2.
  • the lamination-free rubber stopper of Comparative Example has some items not satisfying the standards, as shown in Tables 1 and 2. Since PE, PP, PET and fluoro resins are not soluble in solvents (e.g. n-hexane), no thin resin film can be formed from these resins in the form of solutions.
  • solvents e.g. n-hexane
  • the cyclic resin of the present invention was compressed by two rolls or a press at a temperature of 100 to 140 °C to form a film of 0.3 to 0.4 mm in thcikness.
  • Formation of a slidable laminated rubber stopper was carried out by a method comprising laminating a rubber with the resin film of the present invention simultaneously with vulcanization and shaping of the rubber, specifically using a lower metal mold having a hollow part corresponding to the stopper and an upper metal mold having an end protrusion of a push rod.
  • the resin film of the present invention was placed on the surface of the lower metal mold, on which the foregoing compounded rubber of BR was placed in the form of a sheet, and then the upper metal mold was superimposed thereon, followed by compressing at a temperature of 160 °C and about 80 kg/cm2, thus obtaining a resin film-laminated slidable stopper (Fig. 4 and Fig. 5).
  • Laminated slidable stoppers (comparative articles) were obtained in the similar manner to described above using the same metal molds and the same compounded rubber of BR as dsecribed above and using films of PE, PP and fluoro resin (referred to as F).
  • PE and F met with breakage of the films during shaping and PP (Comparative Example 3) exhibited good shaping property, but occurrence of water foams in the treatment with steam.
  • a rubber stopper as shown in Fig. 7 and Fig. 8 was obtained by laminating both the surfaces of a leg part 15 (in contact with a liquid medicament in a container) and a flange part 17 with the cyclic resin film 1 of the present invention according to the technique described in Japanese Patent Laid-Open Publication No. 272134/1986.
  • this rubber stopper for freeze drying of a pharmaceutical chemical in a container, there was no fear of contamination due to rubber fragmentation caused by movement of the rubber stopper.
  • a stopper bonded to a plastic vessel was prepared by laminating a rubber surface to be contacted with a liquid medicament with the cyclic resin film of the present invention, as shown in Fig. 3, according to the technique described in Japanese Patent Laid-Open Publication No. 1275/1990.
  • the feature of the rubber article of this type consists in that a high quality liquid medicament can be given to the human body without contamination of the medicament.
  • the present invention provides a novel saniatry rubber article in which a rubber surface is laminated with the specified cyclic resin according to the present invention and which has the following features:

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Vascular Medicine (AREA)
  • Hematology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Anesthesiology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Table Devices Or Equipment (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
EP19920300731 1991-01-30 1992-01-29 Objet en caoutchouc revêtu pour applications sanitaires Expired - Lifetime EP0497567B1 (fr)

Applications Claiming Priority (4)

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JP27657/91 1991-01-30
JP2765791 1991-01-30
JP3336690A JP2895293B2 (ja) 1991-01-30 1991-12-19 積層した衛生ゴム製品
JP336690/91 1991-12-19

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EP0559146A1 (fr) * 1992-03-03 1993-09-08 Nippon Zeon Co., Ltd. Instrument médical, composition de polymère et matériau optique
US6007520A (en) * 1992-02-12 1999-12-28 Daikyo Gomu Seiko, Ltd. Medical instrument
EP1092441A1 (fr) * 1998-06-29 2001-04-18 Bracco International B.V. Joint de seringue chargee et seringue chargee
US6255396B1 (en) 1999-09-09 2001-07-03 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
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US8545435B2 (en) 2002-01-03 2013-10-01 Baxter International, Inc. Method and apparatus for providing medical treatment therapy based on calculated demand
US8551045B2 (en) 2006-04-19 2013-10-08 Novo Nordisk A/S Fluid infusion system, a method of assembling such system and drug reservoir for use in the system
US8558964B2 (en) 2007-02-15 2013-10-15 Baxter International Inc. Dialysis system having display with electromagnetic compliance (“EMC”) seal
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JP3198065B2 (ja) 1996-08-19 2001-08-13 株式会社大協精工 衛生品用容器
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US6558628B1 (en) * 1999-03-05 2003-05-06 Specialty Silicone Products, Inc. Compartment cover, kit and method for forming the same
JP3908895B2 (ja) 1999-07-12 2007-04-25 株式会社大協精工 ゴム栓の製造方法
US6297322B1 (en) 1999-09-09 2001-10-02 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
US6743523B1 (en) 2000-03-16 2004-06-01 Baxter International Inc. Multiple layer film of a new non-PVC material
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US7943242B2 (en) 2006-03-30 2011-05-17 Becton, Dickinson And Company Sealing members, articles using the same and methods of reducing sticktion
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US6007520A (en) * 1992-02-12 1999-12-28 Daikyo Gomu Seiko, Ltd. Medical instrument
EP0556034A1 (fr) * 1992-02-12 1993-08-18 Daikyo Gomu Seiko Ltd. Instrument médical
EP0559146A1 (fr) * 1992-03-03 1993-09-08 Nippon Zeon Co., Ltd. Instrument médical, composition de polymère et matériau optique
US5468803A (en) * 1992-03-03 1995-11-21 Nippon Zeon Co. Ltd. Medical implement, polymer composition, and optical material
US5561208A (en) * 1992-03-03 1996-10-01 Nippon Zeon Co., Ltd. Medical implement, polymer composition, and optical material
EP1092441A1 (fr) * 1998-06-29 2001-04-18 Bracco International B.V. Joint de seringue chargee et seringue chargee
EP1092441A4 (fr) * 1998-06-29 2002-08-21 Bracco Int Bv Joint de seringue chargee et seringue chargee
US6632318B1 (en) 1999-09-09 2003-10-14 Baxter International Inc. Method for solvent bonding polyolefins
US6255396B1 (en) 1999-09-09 2001-07-03 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
US6590033B2 (en) 1999-09-09 2003-07-08 Baxter International Inc. Cycloolefin blends and method for solvent bonding polyolefins
US6613187B1 (en) 1999-09-09 2003-09-02 Baxter International Inc Solvent bonding method for polyolefin materials
US10322224B2 (en) 2000-02-10 2019-06-18 Baxter International Inc. Apparatus and method for monitoring and controlling a peritoneal dialysis therapy
US8323231B2 (en) 2000-02-10 2012-12-04 Baxter International, Inc. Method and apparatus for monitoring and controlling peritoneal dialysis therapy
US9474842B2 (en) 2000-02-10 2016-10-25 Baxter International Inc. Method and apparatus for monitoring and controlling peritoneal dialysis therapy
WO2002072180A1 (fr) * 2001-03-08 2002-09-19 One Baxter Parkway Corps de seringue polymere et bouchon
US8545435B2 (en) 2002-01-03 2013-10-01 Baxter International, Inc. Method and apparatus for providing medical treatment therapy based on calculated demand
US7744554B2 (en) 2002-12-31 2010-06-29 Baxter International Inc. Cassette alignment and integrity testing for dialysis systems
US8206338B2 (en) 2002-12-31 2012-06-26 Baxter International Inc. Pumping systems for cassette-based dialysis
US8118781B2 (en) 2006-04-19 2012-02-21 Novo Nordisk A/S Fluid infusion system, a method of assembling such system and drug reservoir for use in the system
US8551045B2 (en) 2006-04-19 2013-10-08 Novo Nordisk A/S Fluid infusion system, a method of assembling such system and drug reservoir for use in the system
CN101426546B (zh) * 2006-04-19 2013-12-04 诺沃-诺迪斯克有限公司 输液系统，组装这种系统的方法和用于该系统的药品容器
WO2007118908A1 (fr) * 2006-04-19 2007-10-25 Novo Nordisk A/S Système de perfusion fluide, sa méthode d'assemblage et réservoir à médicament à utiliser le système
US8361023B2 (en) 2007-02-15 2013-01-29 Baxter International Inc. Dialysis system with efficient battery back-up
US7998115B2 (en) * 2007-02-15 2011-08-16 Baxter International Inc. Dialysis system having optical flowrate detection
US8558964B2 (en) 2007-02-15 2013-10-15 Baxter International Inc. Dialysis system having display with electromagnetic compliance (“EMC”) seal
US8870812B2 (en) 2007-02-15 2014-10-28 Baxter International Inc. Dialysis system having video display with ambient light adjustment
US7731689B2 (en) 2007-02-15 2010-06-08 Baxter International Inc. Dialysis system having inductive heating
US9799274B2 (en) 2007-02-15 2017-10-24 Baxter International Inc. Method of controlling medical fluid therapy machine brightness

Also Published As

Publication number Publication date
DE69213489D1 (de) 1996-10-17
US5288560A (en) 1994-02-22
EP0497567B1 (fr) 1996-09-11
EP0497567A3 (en) 1993-01-27
DE69213489T2 (de) 1997-02-06
ATE142558T1 (de) 1996-09-15

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